Structure and dynamics of nanoconfined glass-forming oligomers and diblock coplymers (BPCs) are investigated by a combination of infrared transition moment orientational analysis (IR-TMOA), positron annihilation lifetime spectroscopy (PALS), grazing incidence small angle X-ray scattering (GISAXS), atomic force microscopy (AFM), scanning electron microscopy (SEM) and broadband dielectric spectroscopy (BDS). The oligomers probed are the van der Waals type, tris(2-ethyhexyl)phosphate (TEHP) and the self-associating molecules of 2-ethyl-1-hexanol (2E1H). Symmetric and asymmetric poly(styrene-b-1,4-isoprene) P(S-b-I) are studied for the case of BCPs. The samples are confined either in one-dimensional (1D) in form of thin films or in 2D (nanopores) geometrical constraints. The molecular order of TEHP in nanopores as studied by IR-TMOA shows that about 7% of the molecules are preferentially oriented perpendicular to the long axis of the pores due to their interaction with the pore walls. PALS results reveal that 2E1H confined in nanopores exhibit larger free volume with respect to the bulk. In thin films (1D), P(S-b-I) having volume fraction of isoprene blocks f(PI)= 0.55 exhibits randomly oriented lamellae and their thicknesses are directly proportional to the film thickness d(film). For f(PI) = 0.73, perpendicular cylinders with respect to the substrate are observed for d(film)>50 nm but they lie along the substrate plane when d(film) < 50 nm. In AAO pores (2D) with average pore diameter d(pore) of 150 nm, straight nanorods are formed which change to helical structures in 18 nm pores. Molecular dynamics of 2E1H and TEHP constrained in nanopores (2D), is influenced by the interplay between confinement and surface effects. Confinement effects show up as an increase in the structural relaxation rate with decreasing pore sizes at the vicinity of the glass transition temperature. This is attributed to the reduced packing density of the molecules in pores as quantified by PALS results for 2E1H. Whereas the orientation and morphologies of the domains in P(S-b-I) and the chain dynamics of isoprene chains are influenced by the finite--size and dimensionality of confinement, the segmental motion, related to the dynamic glass transition (DGT) of both styrene and isoprene blocks remains unaffected-in its relaxation time-within experimental accuracy. Effects of nanoscale confinement on the molecular dynamics therefore depend on a number of factors: the type of molecules (polymers, low molecular liquids), interfacial interactions and the dimensionality of the constraining geometries.

Die Pyrolyse ausgewählter Polysiloxane und Poly(chlor)silane erzeugt meso- und mikroporöses SiC, welches als Hochtemperatur-beständiges Material für Filter, Katalysatorträger und Sensoren ein hohes Anwendungspotential besitzt. Der Pyrolyseprozess bis 1500 °C wird thermogravimetrisch und massenspektrometrisch verfolgt und die resultierenden &amp;quot;Bulk&amp;quot;-Pyrolysate mittels DRIFT-Messungen, Elementaranalyse, XRD, N2-Adsorption und FESEM charakterisiert. Zusammensetzung, Kristallinität und Poreneigenschaften des precursorabgeleiteten SiC lassen sich über die Precursorart sowie über die Pyrolysetemperatur und -dauer steuern. Die Poren entstehen je nach Precursor zwischen 1200 und 1500 °C. Im Falle von mesoporösen Pyrolysaten wird die Porenbildung in erster Linie durch die Abgabe gasförmiger Reaktionsprodukte hervorgerufen. Die Porengrößen dieser Produkte liegen zwischen 6 und 12 nm und die spezifische Oberfläche beträgt bis zu 270 m2/g. Bei den mikroporösen Pyrolysaten, gekennzeichnet durch Poren von 1,5 nm Größe und spezifischen Oberflächen bis 530 m2/g, werden die Poreneigenschaften vor allem durch den im Überschuss vorhandenen elementaren Kohlenstoff geprägt.

Structure and dynamics of nanoconfined glass-forming oligomers and diblock coplymers (BPCs) are investigated by a combination of infrared transition moment orientational analysis (IR-TMOA), positron annihilation lifetime spectroscopy (PALS), grazing incidence small angle X-ray scattering (GISAXS), atomic force microscopy (AFM), scanning electron microscopy (SEM) and broadband dielectric spectroscopy (BDS). The oligomers probed are the van der Waals type, tris(2-ethyhexyl)phosphate (TEHP) and the self-associating molecules of 2-ethyl-1-hexanol (2E1H). Symmetric and asymmetric poly(styrene-b-1,4-isoprene) P(S-b-I) are studied for the case of BCPs. The samples are confined either in one-dimensional (1D) in form of thin films or in 2D (nanopores) geometrical constraints. The molecular order of TEHP in nanopores as studied by IR-TMOA shows that about 7% of the molecules are preferentially oriented perpendicular to the long axis of the pores due to their interaction with the pore walls. PALS results reveal that 2E1H confined in nanopores exhibit larger free volume with respect to the bulk. In thin films (1D), P(S-b-I) having volume fraction of isoprene blocks f(PI)= 0.55 exhibits randomly oriented lamellae and their thicknesses are directly proportional to the film thickness d(film). For f(PI) = 0.73, perpendicular cylinders with respect to the substrate are observed for d(film)>50 nm but they lie along the substrate plane when d(film) < 50 nm. In AAO pores (2D) with average pore diameter d(pore) of 150 nm, straight nanorods are formed which change to helical structures in 18 nm pores. Molecular dynamics of 2E1H and TEHP constrained in nanopores (2D), is influenced by the interplay between confinement and surface effects. Confinement effects show up as an increase in the structural relaxation rate with decreasing pore sizes at the vicinity of the glass transition temperature. This is attributed to the reduced packing density of the molecules in pores as quantified by PALS results for 2E1H. Whereas the orientation and morphologies of the domains in P(S-b-I) and the chain dynamics of isoprene chains are influenced by the finite--size and dimensionality of confinement, the segmental motion, related to the dynamic glass transition (DGT) of both styrene and isoprene blocks remains unaffected-in its relaxation time-within experimental accuracy. Effects of nanoscale confinement on the molecular dynamics therefore depend on a number of factors: the type of molecules (polymers, low molecular liquids), interfacial interactions and the dimensionality of the constraining geometries.

Single molecule studies using nanopores have gained attention due to the ability to sense single molecules in aqueous solution without the need to label them. In this study, short DNA molecules and proteins were detected with glass nanopores, whose sensitivity was enhanced by electron reshaping which decreased the nanopore diameter and created geometries with a reduced sensing length. Further, proteins having molecular weights (MW) ranging from 12 kDa to 480 kDa were detected, which showed that their corresponding current peak amplitude changes according to their MW. In the case of the 12 kDa ComEA protein, its DNA-binding properties to an 800 bp long DNA molecule was investigated. Moreover, the influence of the pH on the charge of the protein was demonstrated by showing a change in the translocation direction. This work emphasizes the wide spectrum of detectable molecules using nanopores from glass nanocapillaries, which stand out because of their inexpensive, lithography-free, and rapid manufacturing process

Die Pyrolyse ausgewählter Polysiloxane und Poly(chlor)silane erzeugt meso- und mikroporöses SiC, welches als Hochtemperatur-beständiges Material für Filter, Katalysatorträger und Sensoren ein hohes Anwendungspotential besitzt. Der Pyrolyseprozess bis 1500 °C wird thermogravimetrisch und massenspektrometrisch verfolgt und die resultierenden &amp;quot;Bulk&amp;quot;-Pyrolysate mittels DRIFT-Messungen, Elementaranalyse, XRD, N2-Adsorption und FESEM charakterisiert. Zusammensetzung, Kristallinität und Poreneigenschaften des precursorabgeleiteten SiC lassen sich über die Precursorart sowie über die Pyrolysetemperatur und -dauer steuern. Die Poren entstehen je nach Precursor zwischen 1200 und 1500 °C. Im Falle von mesoporösen Pyrolysaten wird die Porenbildung in erster Linie durch die Abgabe gasförmiger Reaktionsprodukte hervorgerufen. Die Porengrößen dieser Produkte liegen zwischen 6 und 12 nm und die spezifische Oberfläche beträgt bis zu 270 m2/g. Bei den mikroporösen Pyrolysaten, gekennzeichnet durch Poren von 1,5 nm Größe und spezifischen Oberflächen bis 530 m2/g, werden die Poreneigenschaften vor allem durch den im Überschuss vorhandenen elementaren Kohlenstoff geprägt.

No description available.